Textile or the like pestproofing medium and use



I Patented 23, 1938 1 UNITED STATES on. m m ms'rrnoor'md msnwuann Us]:

um Martin, Basel, Switserland, alalgnor to theflnn o! I. IL Geigy 8. A" Basel, Swltlcr- No Drawing Application mm." 2a, 1031. soits? No. 123.061. In Germany, February 7L i 11 cums (01. 161-31) It has been found that compounds which contain the live or six'sided atomic ring group 00 \ofi-co-n 2* 0 I in the molecule are valuable insect combatting agents.

In the above formula:

x represents a single or double membered, saturated or unsaturated, unsubstituted or substituted carbon bridge which closes the ring and can at the same time be a. member of further ring systems, and

R represents 0-alkyl. --O-aralkyl, '--NH:,

NH-alkyl, NH-aryl, NH-- and N =cycloalkyl or corresponding single or mixed substituted tertiary amino groups, ureidoand guanyl radicals, other nitrogen-containing radicals or ring systems, or simple or substi; tuted alkyl-, ar'alkylor aryl groups.

Such compounds are for example: '(1) Tetronic-a-csrboxylic acid ester wherein alkyl is represented by the groups CH1.

C0\ CH/ aCH-CO-CH:

CH: O

o The two methyl groups can also be .one or two phenyl groups. (3) a-Aceto-benzotetronic acid replaced by :OILCO-CH:

- group.

Instead of CH; other alkyl or aralkyl and aryl groups such as ethyl, butyl, amyl, benzyl, phenyl,

' ethyl,- phenyl, p-chlorophenyl may be present.

(4) Benzotet'ronlc-acid-s-carboxylic acid-benzylester wn-co-o-cm-O to 'Ihe'chlorobenzyl, phenylethyl or alkyl radicals from OH: to CsHu may also replace the benzyi (5) Benzotetronic acid-m-carboxylic acid-amide co uCHCO-N H 0 o I a or the custom, CaH-z, CsHo, CsHu amide thereof (6) Benzotetronic acid-a-carboxylic acid-piperidide Y co cur-om )cn-co-n on,

0/ O CHr-CBI The nitrogen atom may bear other divalent cycloalkyl radicals, nicotine or anabasine being employed in the place of piperidine.

(7) Benzotetronic acid-u-carbonylic acid-ureide co acn-co nnco-Nm (8) Benzotetronic acid a carboxylic acidguanidide aCH-CO-NH-f-( -NE o H s (9) Benzotetronic acid-a-carboxylicacld-anilide Instead of the phemrlradlcal there may be mentioned tolyl, unsubstituted or substituted aminophenyl, monoor dichloro-phenyl, -/p-naphtbyl,

cyclohexyl, methyl-cyclohexyl, diethylaminoethylene and similar radicals.

(10) Benzotetronic acid-a-carboxylic acidmethylanllide CO CH:

aCH-C ON The phenylradical may also be substituted by one or more halogen atoms.

(12) 2.3 naphthotetronic acid a carboxylic acid-ester v acid-a-carboxylic acid The alkyl group may vary from CH: to CsHn.'

The atom grouping is an essential part of all these compounds, X being a single or two membered carbon bridge. Through the substitution by three CO groups, the hydrogen atom of the a-carbon atom becomes very reactive, wherefore compounds of this kind have a strongly acid character. They therefore dissolve easily in alkalies and can be precipitated again by the addition of strong acids. By suitable substitution in the groups linked to the above typical atom grouping the solubility in water or organic solvents can be altered and the physiological effectiveness influenced. In particular amino or halogen substituents in the aromatic and aliphatic side groups have notable influence.

Substituted condensation products of unsaturated aromatic hydroxy-acids have already been proposed as insect destroying agents. Under these fall halogen substitution products of cumarine or the homologues thereof or the derivatives thereof, all substances containing a substituted pyrone ring. Fluo-, bromo-, chloro-, alkyl, aryland thio-cumarines are named. The type of compound used in the present process can be termed an a-keto-y-lakton, in which however to obtain remarkable effectiveness an additional -CO-group must be bound to the a-position carbon atom. Chemical consideration of the structure of these curamine derivatives in comparison with the present a-ketotetronic acids (a-carbonyltetronic acids) immediately shows the fundamental difference between them. Dehydracetic acid which is outstandingly effective,

behaves chemically entirely differently from a cumarine. The same applies to the a-kEtOSllbstituted tetronic acids.

' Compared with the cumarine derivatives mentioned above, they are in part notably more ef- 2,127,a're

fective and in par't more bearable to the human skin (according to Anschiitz, Annalen der Chemie. 1909, 887, page 201, halogen cumarines produce blisters on the skin and strong itching) in addition they are quite colourless, which is an advantage over the yellow coloured thiocumarine; the latter feature is particularly important as regards the use of these insect combatting agents on textiles. I

The above mentioned insect combatting agents can be employed by. the usual processes. Solutions in water or in cheap organic solvents can be used for spreading, sprinkling or dipping the materials and textiles to be protected; they can also be atomized without harmful effects being noticed on warm-blooded beings. Pelts, feathers or wool treated with such solutions can be protected in a lasting manner against moths. Precipitation of the effective substance from alkaline solution on to the article to be protected by means of acid leads to the same result. If plant parasites are sprayed it will be found, for example on flies or walking-sticks that the poisoning effeet by contact is very good.

Furthermore, solutions or emulsions in oils,

creams, fats may be used or the compounds may be added to powders or they may be used in any form usual for combatting insects.

The following examples illustrate the invention, the parts being by weight:

Example I 2 parts of dehydracetic acid are dissolved in 98 parts. of alcohol; pelts, feathers or wool are treated for example by dipping, then centrifuged and dried. The goods so treated are moth proof. Quite dilute solutions sumce to obtain a satisfactory protection against moths.

If instead of the above mentioned dehydracetic acid, use be made of derivatives of tetronic acids, such as dichlorbenzoor benzotetronic acidcarboxylic acid ester, for example the methyl-,

ethyl-, propyl-, amyland other esters, or other mentioned a-ketosubstituted tetronic acid derivatives such as ketones, carboxylic acid-amides, -anilides or -diethylethylenediamides, an equivalent effect is obtained.

Certain parasites such as walking-sticks are killed by spraying with the above mentioned alcoholic solutions. good when used as contact agents against flies.

Example II A concentrated aqueous solution of the compounds mentioned in Example I, is made with the aid of alkalies, the material to be treated dipped therein and then acidified, whereby a satisfactory protection against insects is again obtained.

X being a ring closing grouping selected from the groups -cm-, CH-lower alkyl, -CH=(|J- CH=C-, CH| cHl phe'nylene, 'naphthylene, and R. being a mem- The said compounds are. also ber of the group consisting of 0.lower alkyl, --O.arallryl, -N'Hz, NH.lower alkyl, -NI-I.aryl, aryllllower alkyl, -NH and N=cycloalwl.

lower alkyl, aralkyl and phenyl.

2. A devitalizing composition of matter for combatting. pests of the insect class, containing as its essential active ingredient a compound represented by the formula wnJL-R B being a member of the group consisting of O.lower alkyl, 0.aralkyl, NH:, -NH.lower alkyl, -NH.aryl, aryllTlZlower alkyl, N'H- and -N=cycloalky1, lower alkyl, aralkyl and phenyl.

3. A devitalizing composition of matter for combatting pests of the insect class, containing as its essential active ingredient a compound represented by the formula Emma-on R being a member of the group consisting of lower alkyl and aralkyl.

4. A devitalizing composition of matter for combatting pests of the insect class, containing as its essential active ingredient a compound represented by the formula as its essential active ingredient a compound represented by the formula acH-c0-c.ni.+1

n being a number from 1 to 5.

a 6. A devitalizing composition of matter for combatting pests of the insect class, containing as its essential active ingredient a compound represented by the formula on-coo c.H,.+1

n being a number from 1 to 5.

7. A devitalizing composition of matter for combatting pests of the insect class, containingas its essential active ingredient a compound represented by the formula B being a member of the group consisting of zero and CH3.

8. A devitalizins composition of matter for combatting pests of the insect class, containing as its essential active ingredient -acetobenaotetronic acid.

9. A devitalizing composition of matter for combatting pests of the insect class, containing as its essential active ingredient u-carbanilidobenzctetronic acid.

10. A devitalizing composition of matter for combatting pests of the insect class, containing as its essential active ingredient benzotetronic acid ethyl ester.

11. A method of protecting materials against pests of the insect class, comprising treating the materials first with a strong alkaline aqueous solution of a compound named in claim 1 and thereupon with an acid agent.

HENRY MARTIN. 

